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Well-defined linear, 3-, 4-, and 6-arms polyvinylidene fluoride (PVDF) stars are synthesized by reversible addition−fragmentation chain transfer (RAFT) polymerization using mono-, tri-, tetra-, and hexa-functionalized chain transfer agents, respectively, and 1,1-bis-(tert-butylperoxy)-cyclohexane as initiator. The crystallization kinetics and the polymorphic character of PVDF stars are investigated by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) . Using a cooling rate of 10 °C min−1, all samples form α- and β-phases. However, the amount of β-phase increases with respect to the α-phase as the number of arms in the PVDF stars increases. This results from the increased topological complexity in the stars , which leads to the preferential formation of the less thermodynamically stable ferroelectricβ-phase. When the cooling rate is decreased (1 °C min−1) and/or an isothermal crystallization procedure is applied, polymorphism is inhibited in the PVDF stars, and only the paraelectric α-phase is formed. On the other hand, the linear PVDF sample is still capable of producing both paraelectric and ferroelectric phases after slow cooling or isothermal crystallization. The isothermal crystallization kinetics of the PVDF stars i faster than the linear as a result of their speedier nucleation, possibly promoted by their particular topology where the arms radiate from a common junction point., F.A., G.Z., and N.H. thankfully acknowledge the support of King Abdullah University of Science and Technology (KAUST). N.M., J.M., and A.J.M. acknowledge the support of the Basque Government through grant IT1503-22. N.M. thankfully acknowledges his Ph.D. fellowship from the POLYMAT Basque Center for Macromolecular Design and Engineering. J.M. acknowledges partial financial support from the IBERDROLA Foundation.

Trabajo presentado al GEP-SLAP (XVI Reunión del Grupo Especializado de Polímeros GEP de la Real Sociedad Española de Química (RSEQ) y de la Real Sociedad Española de Física (RSEF) - XVII Simposio Latinoamericano de Polímeros), celebrado en San Sebastián (España) del 8 al 12 de mayo de 2022., The authors thank ALBA Synchrotron Light facility for supporting the X-rays experiments at beamline BL11-NCD-SWEET and the funding by ALBA project 2018082953 (2019) and by Mineco MAT2017-83014-C2-1-P. N. M. gratefully acknowledges the financial support from POLYMAT Basque Center for Macromolecular Design and Engineering. J. M. acknowledges support from the Provincial Council of Gipuzkoa under the program Fellow Gipuzkoa and Ayudas a la Investigación 2018, from Fundación IBERDROLA.

In this work, we study how chain topology can induce different polymorphic behaviors in poly(vinylidene fluoride) (PVDF)-based materials. A linear PVDF precursor with two azido groups at the junction point, (PVDFx-N3)2 and three 4-miktoarm star copolymers (PVDFx)2-b-(PEOy)2 with two poly(ethylene oxide) (PEO) and two PVDF arms were synthesized and employed in this study. The amphiphilic miktoarm copolymers were prepared by a combination of anionic ring-opening polymerization, iodine transfer radical polymerization (ITP), and copper-catalyzed azide-alkyne cycloaddition (CuAAC). They have practically similar overall molar mass but different compositions, ideal for performing bulk morphology and crystallization investigations. The isothermal overall crystallization kinetics of the PVDF and PEO arms of the 4-miktoarm star copolymers and representative PEO and PVDF precursors was determined by Differential Scanning Calorimetry (DSC). The results indicate that the star arms crystallized faster than the equivalent precursors as the kinetics are dominated by nucleation effects. The phases formed by the PVDF components in the materials examined were analyzed by studying their melting behavior by DSC, their superstructural morphology by Polarized Light Optical Microscopy (PLOM), and the phase structure by Fourier Transform Infrared Spectroscopy (FTIR). The linear PVDF and (PVDF29-N3)2, exhibited α, β and γ-phases (with a majority of β-phase formation) during melting after isothermal crystallization. The ratio of the different phases depends on the crystallization temperature. An analysis of the multiple melting behavior indicated that the sample forms both α and β-phases initially, and the α-phase partially transforms into the γ-phase during isothermal crystallization when the temperature of crystallization increases. We found a remarkable behavior for the 4-miktoarm star copolymers, as the PVDF arms only form the ferroelectric β-phase when all three materials were isothermally crystallized regardless of the crystallization temperature employed. The presence of the polymorphism in the PVDF was detected by DSC, PLOM, and FTIR. Hence, we have shown that tailoring chain topology in PVDF copolymers can lead to exclusive β-phase formation, a path that can be exploited for future piezoelectric applications., We acknowledge funding from MICINN through grant PID2020-113045GB-C21. We would also like to acknowledge the support of the Basque Government through grant IT1503-22. N. M. thankfully acknowledges his Ph.D. fellowship from the POLYMAT Basque Center for Macromolecular Design and Engineering. J. M. acknowledges partial financial support from the IBERDROLA Foundation. Y.P., G.P., A.P., V.R., and N.H. thankfully acknowledge the support of King Abdullah University of Science and Technology (KAUST).

Snow dynamics are key to understanding tree growth in mountain forests and future response to climate change. However, precise monitoring of microclimate conditions and variables related to tree growth and functioning are lacking. To advance on those issues, snow cover and microclimate conditions, tree phenology, xylogenesis, intra-annual radial growth and the concentration of sapwood and needle non-structural carbohydrates were intensively monitored in four Pinus uncinata forests along an altitudinal gradient over three years in a Pyrenean valley (NE Spain). Snow dynamics exerted strong influence on soil temperature and moisture, particularly before and during the early growing season. Soil temperature was the most relevant microclimate variable during the overall xylogenesis, mainly influencing the production of mature tracheids. Large snow accumulation resulted in later snow depletion and a consequent delay in soil warming onset. Low soil temperatures in the spring, related to prolonged snow persistence, retarded cambial reactivation and led to lower growth rate. Despite strong spatial variability among plots, wood production was determined by snow dynamics in three out of the four studied plots. This study highlights the major role played by early and late growing season soil temperatures on radial growth of mountain conifers. The results of this study suggest that a future shallower and more transitory snowpack in the studied forests, together with warmer soil and air temperatures, may increase radial growth and productivity of similar mid-latitude, young mountain forests., This study was supported by the projects: “Bosque, nieve y recursos hídricos en el Pirineo ante el cambio global” funded by Fundación Iberdrola, CGL2014-52599-P (IBERNIEVE) and CGL2017-82216-R (HIDROIBERNIEVE) funded by the Spanish Ministry of Economy and Competitiveness. ASV was supported by a pre-doctoral University Professor Training grant [FPU16/00902] funded by the Spanish Ministry of Education, Culture and Sports. EAG was supported by a pre-doctoral FPI grant [BES-2015-071466] funded by the Spanish Ministry of Economy and Competitiveness. JJC, AG and MC acknowledge funding by project RTI2018-096884-B-C31 (Spanish Ministry of Economy and Competitiveness).

Semiconductor nanocrystals, used in quantum dot solar cells, are interesting materials for photovoltaics because they can be obtained in solution and can be composed of abundant elements. Moreover, as compared to other photovoltaic materials, nanomaterials show unique features due to their novel size- and shape-dependent properties such as band gap tuning, multiple exciton generation, and modulation of n- or p-type behaviour by doping or by modifying the ligands on the surface of the nanocrystals. Quantum dot solar cells, together with perovskite solar cells, are the latest incorporation to photovoltaic technologies and have already shown impressive progress in efficiencies and great promise as alternatives to commercial solar cells. However, in all cases, the highest efficiencies are obtained with materials that contain lead in their composition. To solve the problem of toxicity, several materials have been proposed as substitutes. In this review, we summarize some of the non-toxic alternatives that have been synthesized as nanocrystals and incorporated in photovoltaic solar cells, specifically: tin (Sn), germanium (Ge), bismuth (Bi), and antimony (Sb)-based materials. Our findings show that this field has been scarcely covered; there are very few reports on non-toxic perovskite nanocrystals incorporated in solar cells and in general, the efficiencies are still modest. However, this area deserves more attention since some nanocrystal-based solar cells already outperform bulk counterparts. For each case, we also discuss factors limiting efficiency, the approaches followed to overcome these limitations, and the possible solutions to improve efficiency., Authors acknowledge Fundación Iberdrola España, CIBER-BBN (financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund), the ICTS “NANBIOSIS”, Agencia Estatal de Investigación-AEI (Ref. PID2019-107893RB-I00 and PID2019-104307GB-I00), and Gobierno de Aragón (Ref. T57_20R and E47_20R) for financial support.

A volume in Solar Cell Engineering., The development of energy-harvesting and energy-storage devices based on renewable sources will be fundamental for the deployment of autonomous or isolated systems like emerging internet-of-things (IoT) applications. This chapter will focus on the use of bismuth nanomaterials in energy-related applications. These materials fulfill the requirements of being composed of abundant and non-toxic elements and therefore can be considered environmentally friendly functional materials. The specific applications that will be covered are: energy-harvesting devices including solar cells and thermoelectrics, electrochemical energy storage devices such as batteries and supercapacitors, and photocatalysts for solar hydrogen production. For each technology, we will discuss the state of the art, challenges, and the focus areas for current research., Authors acknowledge Fundación Iberdrola España; Programa Operativo FEDER Aragón 2014–2020, “Construyendo Europa desde Aragón” (Ref. LMP35_18); and M-ERA.NET network, project "NOEL" (reference PCI2019–103637) funded by the Agencia Estatal de Investigación through the PCI 2019 call.

Thin NiOx layers were prepared by oxidation at 400, 500 and 600 °C of metallic Ni deposited by electron beam evaporation. The bandgap of NiOx determined from optical measurements increases from 3.6 to 3.7 eV with the increase of oxidation temperature from 400 to 500°C. Higher temperature leads to larger grain sizes, 12.6 nm at 400 °C, 15.3 nm at 500 °C and 16.1 nm 600 °C. Photodiodes based on NiOx/Si heterostructure were fabricated by evaporation of semitransparent Au top contacts. The structures with NiOx obtained at 500 °C showed superior diode characteristics compared to the other two types of devices with dark current < 3.5 × 10-8 A (current density J < 3.9 × 10−4 A/cm2) for reverse biases between 0 and -2 V and forward current of 3.3 × 10−5 A (J = 0.36 A/cm2) at bias of 1.5 V. The responsivity of these devices at 0 V is between 0.85 and 0.55 A/W for wavelengths in the 365 – 635 nm range, values higher than those previously reported for self-powered NiOx/Si photodiodes. The responsivity at reverse bias of -1.5 V increases more than 60 times to values of 33, 32, 50 and 59 A/W for red, green, blue, and ultraviolet light, values among the highest reported for broadband photodetectors. The excellent properties of the photodiodes with NiOx obtained at 500 °C are the result of a higher quality of the Si/NiOx interfacial region, which leads to lower recombination rate of the photogenerated carriers., JRC gratefully acknowledges the National Council for Science and Technology (CONACYT), Mexico for a Ph.D. fellowship. MB acknowledges Fundación Iberdrola España, CIBER-BBN, the ICTS “NANBIOSIS”, and Agencia Estatal de Investigación-AEI (PID2019-107893RB-I00) for financial support. This work was partially supported by Proyecto Bilateral Conacyt-AFOSR CC0015-2016-05-279915 “Single Crystal and Thin Film Hybrid Perovskite Materials for Optoelectornic Applications”.

The identification of threats to migratory species of conservation concern and the relevance of protected areas for them is often biased towards breeding areas. The European Roller Coracias garrulus is a long-distance migrant experiencing a pronounced decline throughout its breeding range, which has been attributed to the degradation of open agricultural habitats. However, its conservation status in non-breeding areas in Africa remains unstudied. Land cover change is a major threat affecting migratory birds in their wintering grounds, therefore identifying important areas for their protection at this stage is a priority. Here we used occurrence data during the wintering season and ecological niche models to identify key land cover and areas used by Rollers in Africa. First, we used 33 filtered locations from six satellite-tracked birds breeding in Spain to describe suitable wintering areas for the Spanish population (westernmost part of the Eurasian breeding range). We also used 1,167 occurrence data in southern Africa from open-access databases and bird atlases to characterise the overall wintering range of the species. The Spanish population occupied a relatively small area in the north-western part of southern Africa, and a narrow range of land covers. Open grassland, less steep areas and those with sparse tree cover are correlated with suitability. In all, 18.06% of suitable wintering areas for the Spanish population overlapped with protected areas. The overall population of Rollers occupied a wider area and range of land cover. Tree cover was the most important variable affecting suitability, with areas without tree cover being the least suitable. We found that 9.58% of suitable wintering areas for the overall population overlapped with protected areas. Our results suggest that Rollers from different origins (breeding populations) use separate, but overlapping, wintering areas and may have different habitat requirements, and therefore, population-specific conservation strategies in these areas might be needed to fully protect the species., DP and JMA were funded by the Spanish Ministry of Education and Science/FEDER through the projects CGL2008-00718 and by the Government of Extremadura through the project TA13002 to DP. All the information about tagged Rollers in Spain has been obtained in the framework of the ‘Migra’ program (www.migraciondeaves.org/en/) developed by SEO/BirdLife, coordinated by Juan Carlos del Moral, and financed by Iberdrola Foundation. The Extremadura Regional Government provided information on one individual

9 páginas.-- 4 figuras.-- 3 tablas.-- 5 referencias.-- Supplementary data related to this article can be found at http://dx.doi.org/10.1016/j.chemosphere.2017.08.063, Establishing energy crops could be a cost-efficient alternative towards the valorization of the plant biomass produced in contaminated lands, where they would not compete with food production for land use. Dittrichia viscosa and Silybum marianum are two native Mediterranean species recently identified as potential energy crops for degraded lands. Here, we present the first characterization of the decomposition of the biomass of these species during thermo-chemical conversion (pyrolysis). Using a greenhouse study we evaluated whether the quality of D. viscosa and S. marianum biomass for energy production through pyrolysis could be substantially influenced by the presence of high concentrations of soluble trace element concentrations in the growing substrate. For each species, biomass produced in two different soil types (with contrasted trace element concentrations and pH) had similar elemental composition. Behavior during thermal decomposition, activation energies and concentrations of pyrolysis gases were also similar between both types of soils. Average activation energy values were 295 and 300 kJ mol−1 (for a conversion value of α = 0.5) for S. marianum and D. viscosa, respectively. Results suggest that there were no major effects of soil growing conditions on the properties of the biomass as raw material for pyrolysis, and confirm the interest of these species as energy crops for Mediterranean contaminated lands., This work was supported by the Iberdrola Foundation (Young Researchers Program) and the Spanish Ministry of Economy and Competitiveness (AGL2014-55717-R project and CTQ2013-46804-C2-1-R projects). We are grateful to Patricia Puente and Cristina García for their help at different stages of the study. MTD was supported by a Juan de la Cierva Postdoctoral fellowship from the Spanish Ministry of Economy and Competitiveness, and a postdoctoral fellowship from University of Seville (V Plan Propio).

Novel (PVDF)2-b-(PEO)2 4-miktoarm star copolymers (PVDF: polyvinylidene fluoride, PEO: polyethylene oxide) with three different compositions, but the same overall molecular weight, were synthesized by combining iodine transfer and anionic polymerizations with “click” chemistry. We have studied the polymorphic character of the PVDF arm crystals in the 4-miktoarm star copolymers in comparison with one of their 2-arm star (linear) precursors ((PVDF29-N3)2), when the samples are cooled from the melt at different cooling rates. The phase behaviour was investigated by small angle X-ray scattering (SAXS) and polarized light optical microscopy (PLOM). The results indicate that the materials are either weakly segregated in the melt or melt-mixed. They form PVDF spherulites at high crystallization temperatures when the PEO component is molten. The relative contributions of the α and β-phase were determined by in situ wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy. All samples exhibit a mixture of α and β-phase crystals when cooled from the melt at 20 °C min−1. However, the amount of β-phase is much larger in the 4-miktoarm star copolymer samples than in the (PVDF29-N3)2 linear precursor. Therefore, the 4-miktoarm star chain topology was found to induce β-phase formation. As the samples are cooled at slower rates, the amount of PVDF β-phase crystals increased. For samples crystallized at 1 °C min−1, the PVDF arms of all the synthesized (PVDF)2-b-(PEO)2 miktoarm star copolymers form exclusively the ferroelectric/piezoelectric β-phase crystals. Therefore, these materials have potential applications in the field of energy harvesting., N. M. thankfully acknowledges his PhD fellowship from the POLYMAT Basque Center for Macromolecular Design and Engineering. J. M. acknowledges partial financial support from the IBERDROLA Foundation. We acknowledge funding from MINECO MAT2017-83014-C2-1-P project and from the Basque Government through grant IT1309-19.

Esta monografía constituye la quinta publicación técnica del programa Migra de SEO/BirdLife (www. migraciondeaves.org)., [ES]: Esta publicación trata sobre la ecología del movimiento de la cigüeña blanca (Ciconia ciconia) a lo largo de todo el ciclo anual: temporadas de cría y de invernada y ambas migraciones entre estas zonas. Se trata de la quinta monografía del programa Migra (www.migraciondeaves.org) desarrollado por SEO/BirdLife desde 2011, cuyo objetivo es conocer los movimientos y la migración de las aves presentes en España, y que para el estudio de esta especie ha contado con la colaboración de la organización suiza Storch Schweiz, la Estación Biológica de Doñana (EBD-CSIC), el Instituto MaxPlanck de Ornitología en Radolfzell (Alemania) y el Grupo SaBio del IREC (CSIC-UCLM-JCCM). La cigüeña blanca es un ave de gran tamaño, muy planeadora y que depende de las corrientes térmicas para el vuelo. Hasta hace relativamente poco tiempo, era considerada un migrador transahariano obligado que solo se observaba en territorio ibérico durante la época de reproducción. Sin embargo, en las últimas décadas está cambiando su comportamiento migratorio, y en la actualidad se cuenta con un importante número de aves que invernan en España, tanto aves nativas invernantes como ejemplares de origen centroeuropeo. Durante la migración transahariana la península Ibérica representa un área de paso obligado para las cigüeñas blancas de Europa Occidental y centroeuropeas, que viajan hasta el área de Gibraltar para cruzar el Estrecho entre finales de agosto y septiembre, más tarde que las aves ibéricas. Una vez en África continúan la migración atravesando el desierto del Sahara hasta llegar al Sahel, donde se encuentra la principal área de invernada de la población occidental. En España, la población reproductora se distribuye fundamentalmente en la mitad occidental de la Península y en el valle del Ebro. Además, cría en Galicia y en localidades aisladas de la fachada cantábrica, pero falta en grandes áreas de la costa mediterránea y este de la meseta. El último censo nacional corresponde a 2004, cuando el tamaño de la población reproductora española se cifró en 33.217 parejas reproductoras y 31.229 ejemplares invernando., [EN]: The present publication describes the movement ecology of white storks (Ciconia ciconia) across the complete annual cycle: breeding and wintering seasons, and both migratory periods between wintering and breeding grounds. It is the fifth monograph published in the context of the Migra program (www.migraciondeaves.org/en/) run by SEO/BirdLife since 2011 in order to describe the movements and migratory routes of the avian species present in Spain. For this particular species SEO/BirdLife has received collaboration from the Swiss non-governmental organization Storch Schweiz, the Doñana Biological Research Station (EBD-CSIC), the Max-Planck Institute of Ornithology in Radolfzell (Germany), and the Health and Biotechnology Research Group of the Spanish Institute of Game and Wildlife Research (IREC, CSIC-UCLM-JCCM). The white stork is a large conspicuous soaring bird that depends on thermals and air currents for its flights. Until recently it was considered an obligatory trans-Saharan migrant that was only present in the Iberian Peninsula during the breeding season. However the white storks’ migratory behaviour has been changing throughout the past decades and at present a large number of birds winter in Spain, both native resident storks and birds from Central Europe that spend the winter in Spanish territory. During trans-Saharan migration the Iberian Peninsula constitutes an obligatory part of the route of white storks of Western and Central Europe that travel to Gibraltar and cross the strait between the end of August and September, later than storks from the Peninsula. Once in Africa these birds travel onwards crossing the Sahara to reach the Sahel zone, as sub-Saharan Africa is the primary wintering area of the western white stork population. In Spain the breeding population of white storks occupies predominantly the western half of the Iberian Peninsula and the Ebro river valley. In addition, they breed in Galicia and in the Cantabria part of the Atlantic coast, but are absent in large parts of the Mediterranean and the Eastern plateau. The most recent national census from 2004 noted 33,217 breeding pairs and 33,229 wintering individuals., Los datos recogidos en esta monografía se obtuvieron gracias a la financiación obtenida en el marco de los siguientes proyectos: • El Gobierno de La Rioja financió el marcado con emisor satélite GPS de un adulto de cigüeña blanca en La Rioja. • El Ayuntamiento de Vitoria-Gasteiz en el entorno de la “Green Capital”, el Gobierno Vasco y la Diputación Foral de Álava hicieron posible el trabajo de captura y marcaje de un adulto de cigüeña blanca en Álava. • Once de las cigüeñas adultas fueron marcadas con transmisor satélite en el marco de un proyecto para la determinación del papel de la cigüeña blanca en la epidemiología de los virus de influenza aviar de alta y baja patogenicidad, financiado por el Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria (proyecto RTA2011-00088-C03-02), y desarrollado por el Grupo SaBio del IREC (CSIC-UCLM-JCCM). • El trabajo en el área de Doñana fue financiado por el Ministerio de Economía y Competitividad y la Comunidad Europea (proyecto CGL2012-32544 concedido a J. Blas), el Ministerio de Agricultura, Alimentación y Medio Ambiente (Organismo Autónomo Parques Nacionales, subvención 511/2012 a J. Blas), la Universidad de Saskatchewan (beca Isabel María López Martínez Memorial concedida a F.T-M), y el Consejo Superior de Investigaciones Científicas CSIC (contrato Ramón y Cajal 2010-07120 y proyecto I-LINK0564 a J. Blas). Estos proyectos permitieron financiar y reforzar las colaboraciones científicas entre la Estación Biológica de Doñana y el Instituto Max-Planck de Ornitología en Radolfzell (Alemania) para el estudio de la ecología de las cigüeñas en el sur de España. • La organización suiza Storch Schweiz ha financiado el marcaje de numerosas cigüeñas blancas en España y Centroeuropa dentro del proyecto conjunto “SOS Cigüeña-Migración en cambio” entre esta entidad y SEO/BirdLife. Los trabajos de captura, marcaje y seguimiento de las aves, y las labores de edición y maquetación de esta publicación se han llevado a cabo en el marco de este programa, cuyo principal financiador es la Fundación Iberdrola España.

International audience; Low-losses and directionality effects exhibited by High Refractive Index Dielectric particles make them attractive for applications where radiation direction control is relevant. For instance, isolated metallo-dielectric core-shell particles or aggregates (dimers) of High Refractive Index Dielectric particles have been proposed for building operational switching devices. Also, the possibility of using isolated High Refractive Index Dielectric particles for optimizing solar cells performance has been explored. Here, we present experimental evidence in the microwave range, that a High Refractive Index Dielectric dimer of spherical particles is more efficient for redirecting the incident radiation in the forward direction than the isolated case. In fact, we report two spectral regions in the dipolar spectral range where the incident intensity is mostly scattered in the forward direction. They correspond to the Zero-Backward condition (also observed for isolated particles) and to a new condition, denoted as " near Zero-Backward " condition, which comes from the interaction effects between the particles. The proposed configuration has implications in solar energy harvesting devices and in radiation guiding. Solar energy constitutes one of the most important renewable energy sources. Its clean and non-polluting energy can be converted into electricity by photovoltaic devices like solar cells, which have become a powerful alternative for solving the problem of climate change. However, the high manufacturing costs due to thicknesses of crystalline silicon wafer (typically 200–300 µm), which they are made of, make them not fully competitive with the actual fossil fuel energy resources. For decreasing expenses, thin-film solar cells, whose thickness is about 1–2 µm, have been proposed 1. Nevertheless, one of their main disadvantages is the low absorbance of the incident radiation. In order to increase their efficiency, the use of subwavelength metallic particles on top of the photosensitive surface has been suggested 2,3. Indeed, when incident light illuminates a small metallic particle, free electrons start to oscillate to the same frequency as the incident radiation. These coherent oscillations of the electron plasma depend on the material properties, the particle size and shape, and on the wavelength of the incoming radiation and result in particular surface charge distributions 4. At the resonant frequencies, enhancements of the electric field can be observed in the particle surroundings 5. This phenomenon has been exploited in many different applications like surface enhanced Raman spectroscopy (SERS), or photovoltaic devices among others 1–3,6–11. Therefore, this kind of nanostructures can enhance the absorption of the incident radiation by means of two different mechanisms 1. On one hand, metallic particles can help to couple the incident radiation into the substrate leading to an increment of the absorbed radiation. This is mainly due to the angular spread acquired by the scattered light in the dielectric, so the optical path length of the radiation in the photosensitive volume increases 1. On the other hand, strong enhancements of the electric field in the particle surroundings stimulate the absorption of the incident radiation in the semiconductor wafer 1. However, in spite of the good response of metallic particles in infrared (IR) and visible (VIS) spectral regions 12 , due to the Joule's effect and consequently, to their inherent ohmic losses, the major part of the incident radiation is converted into heating. These photons do not generate electron-hole pairs and, in consequence, do not contribute to increase the electric current. This fact limits the utility of metallic particles in energy harvesting applications.

Here, we report a simple method to produce hierarchically shaped polymeric one-dimensional nanostructures. More specifically, dual-sized polymer nanowires are fabricated employing multibranched anodic aluminum oxide templates. By fine selection of the anodization conditions, we achieve branched nanopores having a first segment of 400 nm in diameter from which seven further 55 nm in diameter pores arise. Wetting of such nanopores with polymer melts - for example, poly(μ-caprolactone) and polystyrene - allows for the nanomolding of their respective inverse nanostructures, that is, dual-sized multibranched polymer nanowires that, when supported on a flat surface, strongly resemble the spatulae of geckos' toes. The structural features of the dual-sized polymer nanostructures, namely, crystalline phase, crystallinity, texture, and so on, are furthermore characterized and interpreted within the context of polymer phase transitions in confined media. Our work presents a readily applicable approach to produce soft nanomaterials of high morphological complexity, thereby with promising implications in the nanotechnology area, for example, in biomimetic solid adhesion., Financial support from the Spanish Ministerio de Ciencia, Innovación e Universidades under projects MAT2014-53437- C2 and MAT2017-83014-C2-2-P is acknowledged. J.M. thanks MEC for the Ramón y Cajal contract and Fundación Iberdrola (Ayudas a la Investigación en Energía y Medio Ambiente 2017) for the financial support.

The performance of polymeric semiconductors is profoundly affected by the thermodynamic state of its crystalline and amorphous fractions and how they affect the optoelectronic properties. While intense research has been conducted on the crystalline features, fundamental understanding of the amorphous fraction(s) is still lacking. Here, we employ fast scanning calorimetry to provide insights on the glass transition of the archetypal conjugated polymer poly(3-hexylthiophene) (P3HT). According to the conceptual definition of the glass transition temperature (T), that is, the temperature marking the crossover from the melt in metastable equilibrium to the nonequilibrium glass, an enthalpy relaxation should be observed by calorimetry when the glass is aged below T. Thus, we are able to identify the enthalpy relaxations of mobile and rigid amorphous fractions (MAF and RAF, respectively) of P3HT and to determine their respective T. Our work moreover highlights that the RAF should be included in structural models when establishing structure/property interrelationships of polymer semiconductors., J.M. acknowledges support from the Diputacion de Guipuzcoa under the programme Fellow Gipuzkoa. Likewise, J.M. thanks MEC for the Ramon y Cajal contract and the Ikerbasque Foundation for the Ikerbasque Research Fellow program. Financial support from Fundacion Iberdrola (Ayudas a la Investigacion en Energia y Medio Ambiente 2017) is also acknowledged. D.C. acknowledges the University of the Basque Country and Basque Country Government (Ref. No. IT-654-13 (GV)), Depto. Educacion, Universidades e investigacion; and Spanish Government (Grant No. MAT2015-63704-P, (MINECO/FEDER, UE)) for their financial support.

[Background] Von Hippel-Lindau (VHL) disease is a rare oncological disease with an incidence of 1:36,000, and is characterized by the growth of different types of tumours. Haemangioblastomas in the central nervous system (CNS) and retina, renal carcinoma and pheochromocytomas are the most common tumours. The absence of treatment for VHL leads to the need of repeated surgeries as the only option for these patients. Targeting VHL-derived tumours with drugs with reduced side effects is urgent to avoid repeated CNS surgeries. Recent reports have demonstrated that propranolol, a β-blocker used for the treatment of hypertension and other cardiac and neurological diseases, is the best option for infantile hemangioma (IH). Propranolol could be an efficient treatment to control haemangioblastoma growth in VHL disease given its antiangiogenic effects that were recently demonstrated by us. The main objective of the present study was the assessment of the efficacy and safety of propranolol on retinal haemangioblastoma in von Hippel-Lindau disease (VHL)., [Methods] 7 VHL patients, from different regions of Spain, affected from juxtapapillary or peripheral haemangioblastomas were administered 120 mg propranolol daily. Patients were evaluated every 3 months for 12 months, at Virgen de la Salud Hospital (Toledo). The patients had juxtapapillary or peripheral haemangioblastomas but had refused standard treatments., [Results] Propranolol was initiated with a progressive increase up to a final dose of 120 mg daily. All tumours remained stable, and no new tumours appeared. The reabsorption of retinal exudation was noted in the two patients having exudates. No adverse effects were recorded. VEGF and miRNA 210 levels were monitored in the plasma of patients as possible biomarkers of VHL. These levels decreased in all cases from the first month of treatment., [Conclusions] Although more studies are necessary, the results of this work suggest that propranolol is a drug to be considered in the treatment of VHL patients with retinal haemangioblastomas. VEGF and miRNA 210 could be used as biomarkers of the VHL disease activity., [Trial registration] The study has a clinical trial design and was registered at EU Clinical Trials Register and Spanish Clinical Studies Registry, EudraCT Number: 2014–003671-30 . Registered 2 September 2014., This work was supported by grants SAF2011–23475 and SAF2014–52374-R from Ministerio de Economía y Competitividad, from Alianza VHL Spain, Fundación Iberdrola, Bodegas Protos and Fundación Port Aventura. Virginia Albiñana was supported by Alianza VHL Spain.

6 p.-3 fig.-1 tab., Background von Hippel-Lindau disease (VHL) is a multisystem cancer syndrome caused by mutations in the VHL gene. Retinal hemangioblastoma is one of the most common tumours, and when it appears near the optic nerve, its treatment is challenging and risky. To date, no treatment has proven effective in changing the course of the disease. This study was designed to evaluate the safety and effectiveness of propranolol in controlling these tumours., Methods Seven patients were included. All patients took a daily dose of 120 mg of propranolol for 1 year. Clinical variables were assessed at baseline, and at 1, 3, 6, 9 and 12 months. The primary endpoint of the study was the number and size of retinal hemangioblastomas. On every visit, retinal outcomes and blood biomarkers (such as vascular endothelial growth factor (VEGF) and miR210) were analysed., Results Number and size of retinal hemangioblastomas remained stable in all patients. All of them had initially increased levels of VEGF and miR210. There was a gradual reabsorption of retinal exudation in two patients, correlating with a progressive decrease of both biomarkers. The only adverse effect reported was hypotension in one patient., Conclusions Propranolol could be used to treat retinal hemangioblastomas in VHL patients, although more studies are needed to determine the ideal dose and long-term effect. VEGF and miR210 should be explored as biomarkers of disease activity. As far as we know, these are the first biomarkers proposed to monitor the VHL disease activity., This clinical trial was supported by grants from Alianza VHL Spain,Fundación Iberdrola, Bodegas Protos and Fundación Port Aventura. Alianza VHL informed the families about the clinical trial for the recruitment of patients,performed the administrative procedures for authorisation and monitoring and financed the travel expenses of the patients for the visits.

Protected areas (PAs) are intended to provide native biodiversity and habitats with a refuge against the impacts of global change, particularly acting as natural filters against biological invasions. In practice, however, it is unknown how effective PAs will be in shielding native species from invasions under projected climate change. Here, we investigate the current and future potential distributions of 100 of the most invasive terrestrial, freshwater, and marine species in Europe. We use this information to evaluate the combined threat posed by climate change and invasions to existing PAs and the most susceptible species they shelter. We found that only a quarter of Europe's marine and terrestrial areas protected over the last 100 years have been colonized by any of the invaders investigated, despite offering climatically suitable conditions for invasion. In addition, hotspots of invasive species and the most susceptible native species to their establishment do not match at large continental scales. Furthermore, the predicted richness of invaders is 11%¿18% significantly lower inside PAs than outside them. Invasive species are rare in long-established national parks and nature reserves, which are actively protected and often located in remote and pristine regions with very low human density. In contrast, the richness of invasive species is high in the more recently designated Natura 2000 sites, which are subject to high human accessibility. This situation may change in the future, since our models anticipate important shifts in species ranges toward the north and east of Europe at unprecedented rates of 14¿55 km/decade, depending on taxonomic group and scenario. This may seriously compromise the conservation of biodiversity and ecosystem services. This study is the first comprehensive assessment of the resistance that PAs provide against biological invasions and climate change on a continental scale and illustrates their strategic value in safeguarding native biodiversity., Research was supported by the Spanish Program of R+D+I (JCI‐2012‐11908, SEV‐2012‐0262, CGL2014‐55145‐R, CGL2015‐65346R, and CGL2009‐7515), Iberdrola Foundation (2014 Energy and Environment Scholarships), the Czech Science Foundation (project no. 14‐36079G, Centre of Excellence PLADIAS), The Czech Academy of Sciences (project RVO 67985939), and the European Community's Seventh Framework Programme FP7/2007‐2013 (grant agreement no. 281422, TEEMBIO). This research contributes to COST Action Alien Challenge (TD1209).

11 páginas.-- 10 figuras.-- 2 tablas.--82 referencias.-- Supplementary data to this article can be found online at http://dx.doi.org/10.1016/j.scitotenv.2017.03.018, The establishment of energy crops could be an option for the management of degraded and contaminated lands, where they would not compete with food production for land use. Here, we aimed to explore the potential of certain native Mediterranean species for the revegetation of contaminated lands for energy production purposes. A field survey was conducted in a trace-element (TE) contaminated area from SW Spain, where the patterns of biomass production, TE accumulation and the calorific value of some thistle species were analyzed along a soil contamination gradient. In a greenhouse experiment the response of two thistle species (Cynara cardunculus and Silybum marianum) and the shrub Dittrichia viscosa to soil contamination was assessed, as well as the effects of these species on some soil microbial parameters involved in nutrient cycling (enzyme activities and arbuscular mycorrhizal colonization in roots). Silybum marianum was able to colonize highly contaminated soils. Its aboveground biomass accumulated Cd and had a relatively high calorific value; this value was similar in biomass obtained from both heavily and moderately contaminated soils. Greenhouse experiment confirmed that S. marianum biomass production and calorific value is scarcely affected by soil contamination. In addition, some soil enzyme activities were clearly enhanced in the S. marianum rhizosphere. Dittrichia viscosa is another promising species, given its capacity to produce a high biomass with appreciable calorific value in acid contaminated soils. Germination of both species was hampered in the acid contaminated soil, and therefore soil pH correction would have to be accomplished before establishing these species on extremely acid soils. Further assessment of the risk of transfer of Cd and other TE to the food chain would be needed to confirm the suitability of these species for the revegetation of contaminated lands with energy production purposes., This work was supported by the Iberdrola Fundation (Young Researchers Program) and the Spanish Ministry of Economy and Competitiveness (AGL2014-55717-R project). MTD was supported by a Juan de la Cierva Postdoctoral fellowship from the Spanish Ministry of Economy and Competitiveness.

Efficient and sustainable synthesis of MOFs, as nano or microcrystalline powder, is crucial for the development of new applications for these compounds. For this purpose, the synthesis of Zn2þ, Cu2þ and Fe3þ-based MOFs was attempted in this study by using a binary medium consisting of supercritical CO2 mixed with an ionic liquid (emimBF4 or emimBr). In comparison with conventional solvothermal and ionothermal synthesis, MOFs were herein obtained under mild reaction conditions, i.e. 200 bar and 65 C, after relatively short reaction periods (, This work was partially financed by the Spanish National Plan of Research CTQ2014-56324-CO2-P1 and MAT2014-53500-R, the Generalitat de Catalunya 2014SGR377 and Fundaci on Iberdrola. Authors acknowledge financial support from the Spanish Ministry of Economy and Competitiveness through the “Severo Ochoa” Programme for Centers of Excellence in R&D (SEV-2015-0496). A. L opez-Periago acknowledges the RyC-2012-11588 contract.

A modification of the simplified Distributed Activation Energy Model is proposed to simulate the pyrolysis of biomass under parabolic and exponential temperature increases. The pyrolysis of pine wood, olive kernel, thistle flower and corncob was experimentally studied in a TGA Q500 thermogravimetric analyzer. The results of the measurements of nine different parabolic and exponential temperature increases for each sample were employed to validate the models proposed. The deviation between the experimental TGA measurements and the estimation of the reacted fraction during the pyrolysis of the four samples under parabolic and exponential temperature increases was lower than 5 °C for all the cases studied. The models derived in this work to describe the pyrolysis of biomass with parabolic and exponential temperature increases were found to be in good agreement with the experiments conducted in a thermogravimetric analyzer., The authors express their gratitude to the BIOLAB experimental facility and to the “Programa de movilidad de investigadores en centros de investigación extranjeros (Modalidad A)” from the Carlos III University of Madrid (Spain) for the financial support conceded to Antonio Soria for a research stay at the German Aerospace Center DLR (Stuttgart, Germany) during the summer of 2014. The authors also gratefully acknowledge the financial support provided by Fundación Iberdrola under the “VI Programa de Ayudas a la Investigación en Energía y Medioambiente”. Funding by the combustion and gas turbine technology program (EVG), of Deutsches Zentrum für Luft- und Raumfahrt e. V. (DLR), the German Aerospace Center, is gratefully acknowledged by Elke Goos

AR was supported by the Portuguese Science Foundation (FCT) through a postdoctoral grant (FCT/DFRH/SFRH/BPD/84328/2012). This work has been partly supported by Iberdrola Renovables under Contract 4502746576.

Current manufacturing technologies for OLEDs involve the use of expensive high vacuum techniques and call for thermal stability requirements which are not fulfilled by many materials. These problems disappear when the OLED films are deposited directly from solution. In this study, we have designed, synthesized and characterized a novel octacoordinated complex, Tris(1-(4-chlorophenyl)-4,4,4-trifluoro-1,3-butanedionate)mono(bathophenanthroline) europium(III), to be used as a >complex-only> emissive layer in wet-processed OLEDs. Upon excitation in the UV region, very efficient energy transfer from the ligands to Eu3+ takes place, giving rise to intense red emission with very high monochromaticity (R=19), both in powder and as a thin film. The decay times of 754 μs (powder) and 620 μs (thin film) are comparable to those of the most efficient Eu3+ β-diketonate complexes reported to date. The same energy transfer leading to saturated red and narrow emission is also observed in the OLED device (glass/ITO/PEDOT:PSS/[Eu(cbtfa)3(bath)]/Ca/Al) when biased at >5.2 V. Its high quantum efficiency (∼60%), good thermal stability up to 200 °C and adequate thin film forming properties make this material a promising chromophore for cost-effective OLEDs., P. Martín-Ramos thanks Fundación Iberdrola for its financial support. CEMDRX group is grateful to Fundação para a Ciência e a Tecnologia (FCT) for providing funds under grant PTDC/FIS/102284/2008 and PEst-C/FIS/UI0036/2011. Funding by the Spanish Ministerio de Economía y Competitividad (MINECO) under projects MAT2012-37276-C03 and MAT2012-37276-C01 is gratefully acknowledged by the URJC and ICMM groups.